Tetrahydrofurfuryl ether of aminodiphenylamine



UNITED STATES PATENT" OFFICE TETRAHYDROFURFURYL ETHER. F AMINODIPHENYLADIINE Robert P. Parker, Somerville, and (Janis Mabelle Hofmann,Bound Brook, N. J., assignors to American Cyanamid Company, New York, N.Y.,

acorporatlon of Maine No Drawing. Application July 3,1944, 1

Serial No. 543,436 Y 6 Claims. (Cl. 260-345) Thisinvention relates totetrahydrofurfuryloxy in conjunction with the following specificexdiphenylamine derivatives having thefollowing amples which are typicalillustrations thereof.

formula: Example 1 CH:C H: C Hr-CH;

. 10 23 parts of 4'-hydroxy-4-nitro diphenylamine wherein X is a memberof'the group consis in f are dissolved in 50 parts of water by theaddition nitro and amino groups and salts of the latter. of 4.4 parts ofodium hydroxide in a suitable e new p ds where X is amino or itsreaction vessel and the solution is heated to reflux a find theirprincipal u e as intermediates for temperature. 28.2 parts oftetrahydrofurfuryl the production of azo dy T can be diazopara-toluenesulfonate are dropped in slowly and tired and up d wit a w d range of cup in the reaction is completed by refluxing for four wmlwnents but areparticular y important i hours. The reaction mixture is cooled and thethe Productifln of ice C producing a b 4'-tetrahydrofurfuryloxy-4-nitr0diphenylamine blue to violet shades which exhibit superior propisallowed to settle. The supernatant liquor is erties such as fastness toligh heating, washin removed and the crude product is of suiiicient andcracking. purity for direct use.

It is not intended to limit the present inven- Em le 2 tion toany singleprocess of preparing the new mp compounds. A very effective method is bythe H reaction of 4'-bydroxy-4-nitro diphenylamine 5 on, (En-cu e INH,,E2' with the tetrahydrofurfuryl ester of an acid, 2

organic or inorganic. Excellent results are obtained by using the esterof organic sulfonic acids and these are preferred by reason of thesmooth 9.4 parts of the nitro compound as obtained in reaction and highyields obtainable. Example 1 are stirred together with 17.8 parts of Thereaction results in the setting free of the alcohol and 36.9 parts of a45% sodium sulfhyacid portion of the ester, and it is thereforeprefdrate solution and the whole is refluxed until enable to carry outthe reaction in the presence reduction is complete. The addition of '75parts of a suitable acid binding substance. -We have of waterprecipitates an oil which is extracted found that the most efficientacid binding subwith ether. The ether extract is separated from stancesare alkali metal hydroxides or alkoxides the reduction mixture, iswashed by decantation and these are preferred although the inventionwith water and is then treated with 3 parts of is not intended to belimited thereto, other acid concentrated sulfuric acid. An oil isprecipitated binding substances being useful. from the ether solutionwhich is separated and It is an advantage of the present invention that40 is dissolved in 125 parts of water. After claripolar solvents such aswater, alcohols or mixtures fication of the aqueous solution in thepresence of thereof can be used and these rare in fact thepredecolorizing carbon, the neutral sulfate of 4'- ferred solvents. Whenwaterlis used no solvent tetrahydrofurfuryloxy-i-amino diphenylamine isrecovery problem is presented. salted out by the addition of sodiumsulfate.

The reduction of the nitro group to the amino If it is desired toregenerate the free base, this group for the production of the preferredcommay be eifected by neutralization of an aqueous pounds may beeffected under either alkaline or solution of the salt in theconventional manner. acid conditions. The results are good in bothcases, the pH determining whether the amino Example 3 compound isproduced in the form of the free base 60 (53 arts of4'-tetrahydrofurfuryloxy-4-nitro I of a salt in the case of anacidicreducins 8 1 diphenylamlne obtained as in Example 1 are It is anadvant e of e present invention that stirred into parts of hydrochloricacid (1.19) the reduction step is not critical and proceeds and thetemperature is raised to 50 C. While smoothly with good yield. agitatingefficiently 8 parts of 20 mesh tin are The invention will be describedingreater detail 55 added gradually portionwise. When addition iscomplete the reaction temperature is maintained at 80 C. until reductionis complete. After cooling, the stannous chloride double salt of thehydro-chloride of 4' tetrahydrorurfuryloxy 4 aminodiphenylamine isfiltered off.

This product may be used in its double salt form for the production ofazo dyestuffs or it may be liberated from the stannous chloride by thecustomary procedures.

Example 4 3.1 parts of the neutral sulfate salt of4'-tetrahydrofurfuryloxy-4-aminodiphenylamine as obtained in Example 2are dissolved in 35 parts of water and 12 parts of 17% hydrochloric acidare added. The resulting solution is iced to 15 C. and a solution of0.83 part of sodium nitrite in 11 parts of water is slowly added untildiazotization is complete. The resulting diazo solution is clarified byfiltration in the presence of decolorizing carbon at 40 C. and theresulting filtrate is treated with sodium chloride. The precipitateddiazonium chloride derived from4'-tetrahydrofurfuryloxy-l-aminodiphenylamine is separated by filtrationand is dried at low temperature.

Example 5 CHr-CH:

parts of water and while the fabric i eficiently agitated, 5 parts of20% sodium acetate solution are run in.

When full color development is obtained, the fabric is rinsed in warmwater, is cleared at 70 C. in an alkaline solution (3% soda ash and 2%sodium hydroxide) for 2 minutes, then treated at on: on on. eH-orno N=N= ocmen' en,

NH mots NHCONH B0;Na NH 2.3 parts of the dry diazonium chloride obtainedas described in Example 4 are blended by grinding with one part ofmagnesium sulfate dihydrate and one part of anhydrous sodium sulfate toa homogeneous powder.

0.4 part of the color blend is stirred in 2.5 parts of methanol and theslurry is treated with a mixture of 1.5 parts of beta-naphthol in 2.5parts of methanol containing 5.0 parts of pyridine. The mixture changesto a deep blue-black slurry immediately and a thick paste results. Thisis stirred while heated on a steam bath for 10 minutes and is thendiluted with 300 part of water and the solution is made alkaline with 10parts of 20% sodium hydroxide solution. The precipitated pigment isflocculated by digestion on a 4 steam bath, is filtered off, is washedwith hot water and is dried at 55 C.

A deep'blue-black powder results, insoluble in water.

Example 6 The blended diazonium chloride as prepared in Example 5 isused to produce developed dyeings on cotton fabric by the followingprocedure:

. Cotton fabric is treated in alkaline grounding We claim:

70 C. in a /2% soap solution, rinsed in fresh water and dried.

The colors obtained with various ice color coupling components arelisted below:

2-hydroxy-3-naphthoic acid-(2'-ethoxy'- anilide) Reddish shade of blue2-hydroxy- 3 -naphthoic acid-(-2-naphthylamide) Strong greenish blueBis-(acetoacetic) -ortho-tolidide Golden yellow 2-hydroxy-3-carbazolecarboxylic acid- (2-methylanilide) Purple 2-hydroxy-3-naphthoicacid-(4'-chloroanilide) Bright greenish blue Example 7 tized by the slowaddition of 3.5 parts of 10% sodium nitrite solution.

1.4 parts of 5,5-dihydroiw-2,2'-dinaphthylurea-7,7'-disulfonic acid aredissolved in 40 parts of water and 3.1 parts of soda ash are dissolvedin the solution. The temperature is adjusted at 10 C. and the aboveprepared diazo solution is slowly dropped in with eflicient agitation.Coupling is immediate with the formation of a deep blue color. Thesolution is treated with sodium chloridefluntil the dyestuif iscompletely salted out and the dyestufl is isolated by filtration.

After drying at 40 C., a deep blue-black solid is obtained which isreadily soluble in water, yielding a blue solution.

1. Compounds having the following formula:

oar-cm :11, expose-o0 4 Ox.

I a -NH in which X is selected from the group consisting of nitro, aminoand acid addition salts of amino. 2. A compound having the followingformula:

CHrCH| H-C Hr-O NH;

' I NH 3. 4"-tetrahydrofurfuryloxy- 4 -nitro diphenylamine having thefollowing formula:

CHr-CH! 35,0 on-om-o N0:

4. A method of preparing 4'-tetrahydrofurfuryloxy-4-nitro diphenylaminewhich comprises reacting a tetrahydrofurfuryl ester with 4'-hyof an acidbinding substance and mblecting the ultra compound thus produced toreduction of the ultra group to the amino group.

6. A method according to chim 4 in which the ester is betrahydroturmrylpara-toluene sul- ROBERT P( PAR-KER. CORRIS HOFMANN.

I Xounte. with a tetrahydmturturyl ester 1n the presence v

